A sensitive multi-residue method for the determination of 35 micropollutants including pharmaceuticals, iodinated contrast media and pesticides in water.

A sensitive, multi-residue method using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed to determine a representative group of 35 analytes, including corrosion inhibitors, pesticides and pharmaceuticals such as analgesic and anti-inflammatory drugs, five iodinated contrast media, ß-blockers and some of their metabolites and transformation products in water samples. Few other methods are capable of determining such a broad range of contrast media together with other analytes. We studied the parameters affecting the extraction of the target analytes, including sorbent selection and extraction conditions, their chromatographic separation (mobile phase composition and column) and detection conditions using two ionisation sources: electrospray ionisation (ESI) and atmospheric pressure chemical ionisation (APCI). In order to correct matrix effects, a total of 20 surrogate/internal standards were used. ESI was found to have better sensitivity than APCI. Recoveries ranging from 79 to 134 % for tap water and 66 to 144 % for surface water were obtained. Intra-day precision, calculated as relative standard deviation, was below 34 % for tap water and below 21 % for surface water, groundwater and effluent wastewater. Method quantification limits (MQL) were in the low ng L(-1) range, except for the contrast agents iomeprol, amidotrizoic acid and iohexol (22, 25.5 and 17.9 ng L(-1), respectively). Finally, the method was applied to the analysis of 56 real water samples as part of the validation procedure. All of the compounds were detected in at least some of the water samples analysed. Graphical Abstract Multi-residue method for the determination of micropollutants including pharmaceuticals, iodinated contrast media and pesticides in waters by LC-MS/MS.

Environmental fate and behavior of acesulfame in laboratory experiments.

Acesulfame is a widely used artificial sweetener. It can be discharged into surface water by domestic wastewater due to its incomplete retention during wastewater treatment. Concentrations may reach up to 10 µg/L for smaller rivers. State-of-the-art analysis allows the determination of acesulfame traces (0.01 µg/L) and thus a potential tracking of the presence of wastewater in riverbank filtrate. To evaluate the behavior of acesulfame in the aquatic environment, biodegradation and sorption of acesulfame were tested. Batch experiments yielded low sorption for several soils (estimated solid-water distribution coefficient of acesulfame <0.1 L/kg). Biodegradation in a fixed-bed reactor was not observed at environmental concentrations of 9 µg/L in aqueous compost and soil extract (observation period 56 days). Only in diluted effluent of a wastewater treatment plant did biodegradation start, after 17 days of operation, and acesulfame completely fade, within 28 days. Flow-through column experiments indicated conservative behavior of acesulfame (recovery >83%) and long-term observations at different concentration levels yielded no biodegradation. Overall, laboratory experiments demonstrated a conservative behavior of acesulfame under conditions typical for riverbank filtration. However, there are hints for certain settings which favor an adaptation of the microbial community and facilitate a rapid biodegradation of acesulfame.

Effects of boundary conditions on the cleaning efficiency of riverbank filtration and artificial groundwater recharge systems regarding bulk parameters and trace pollutants.

Drinking water is often produced from surface water by riverbank filtration (RBF) or artificial groundwater recharge (AGR). In this study, an AGR system was exemplarily investigated and results were compared with those of RBF systems, in which the effects of redox milieu, temperature and surface water discharge on the cleaning efficiency were evaluated. Besides bulk parameters such as DOC (dissolved organic carbon), organic trace pollutants including iodinated X-ray contrast media, personal care products, complexing agents, and pharmaceuticals were investigated. At all studied sites, levels of TOC (total organic carbon), DOC, AOX (adsorbable organic halides), SAC (spectral absorption coefficient at 254 nm), and turbidity were reduced significantly. DOC removal was stimulated at higher groundwater temperatures during AGR. Several substances were generally easily removable during both AGR and RBF, regardless of the site, season, discharge or redox regime. For some more refractory substances, however, removal efficiency turned out to be significantly influenced by redox conditions.

Correlation of six anthropogenic markers in wastewater, surface water, bank filtrate, and soil aquifer treatment.

Six trace contaminants (acesulfame (ACE), sucralose (SUC), carbamazepine (CBZ), diatrizoic acid (DTA), 1H-benzotriazole (BTZ) and its 4-methyl analogue (4-TTri)) were traced from wastewater treatment plants (WWTPs) to receiving waters and further to riverbank filtration (RBF) wells to evaluate their prediction power as potential wastewater markers. Furthermore, the persistence of some compounds was investigated in advanced wastewater treatment by soil aquifer treatment (SAT). During wastewater treatment in four conventional activated sludge WWTPs ACE, SUC, and CBZ showed a pronounced stability expressed by stable concentration ratios in influent (in) and effluent (out) (ACE/CBZ: in45, out40; SUC/CBZ: in1.8, out1.7; and ACE/SUC: in24, out24). In a fifth WWTP, additional treatment with powdered activated carbon led to a strong elimination of CBZ, BTZ, and 4-TTri of about 80% and consequently to a distinctive shift of their ratios with unaffected compounds. Data from a seven month monitoring program at seven sampling locations at the rivers Rhine and Main in Germany revealed the best concentration correlation for ACE and CBZ (r(2) = 0.94) and also a good correlation of ACE and CBZ concentrations to BTZ and 4-TTri levels (r(2) = 0.66 to 0.82). The comparison of ratios at different sampling sites allowed for the identification of a CBZ point source. Furthermore, in Switzerland a higher consumption of SUC compared to Germany can be assumed, as a steadily increasing ACE/SUC ratio along the river Rhine was observed. In RBF wells a good correlation (r(2) = 0.85) was again observed for ACE and CBZ. Both also showed the highest stability at a prolonged residence time in the subsurface of a SAT field. In the most peripheral wells ACE and CBZ were still detected with mean values higher than 36 µg L(-1) and 1.3 µg L(-1), respectively. Although SUC concentrations in wastewater used for SAT decreased by more than 80% from about 18 µg L(-1) to 2.1 µg L(-1) and 3.5 µg L(-1) in these outlying wells, the compound was still adequate to indicate a wastewater impact in a qualitative way.

Occurrence of the antidiabetic drug metformin in sewage and surface waters in Germany.

The antidiabetic drug metformin is among the pharmaceuticals with the highest production numbers world-wide. This paper presents first data on the occurrence of metformin in sewage and surface waters in Germany. Analysis of metformin is based on pre-concentration of the analyte onto a polymeric solid-phase material and subsequent determination by liquid chromatography and tandem mass spectrometry. Applying the method to sewage and surface waters, recoveries >90% and limits of detection of 10 ng L(-1) could be achieved by pre-concentration of a sample volume of only 10 mL. Measurements in sewage and surface waters showed an almost ubiquitous presence of metformin in the aquatic environment. The measured concentration levels in sewage treatment plant influents correlate nicely to the prescription numbers for metformin in Germany. During sewage treatment a significant reduction of metformin concentrations was observed which seems to be mainly due to microbial degradation. Despite this significant elimination during sewage treatment, metformin was found in all river waters under investigation. Concentration levels depend on the sewage fraction of the receiving waters and for most rivers are in the range of several 100 ng L(-1), i.e. in the same order of magnitude or even higher than for other relevant pharmaceutical residues.

Robust trace analysis of polar (C2-C8) perfluorinated carboxylic acids by liquid chromatography-tandem mass spectrometry: method development and application to surface water, groundwater and drinking water.

A simple and robust analytical method for the determination of perfluorinated carboxylic acids (PFCAs) with C2 to C8 chains, based on solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS), was developed, validated and applied to tap water, groundwater and surface water. Two stationary phases for LC (Obelisc N and Kinetex C18) and two materials with weak anion-exchange properties for SPE (Strata X-AW and Oasis WAX) were evaluated. Robust separation and retention was achieved with the reversed phase column and an acidic eluent. Quantitative extraction recoveries were generally achieved for PFCAs with C > 3, but extraction efficiencies were different for the two shortest chained analytes: 36 to 114% of perfluoropropanoate (PFPrA) and 14 to 99% of trifluoroacetate (TFA) were recovered with Strata X-AW, while 93 to 103% of PFPrA and 40 to 103% of TFA were recovered with Oasis WAX. The sample pH was identified as a key parameter in the extraction process. One-step elution-filtration was introduced in the workflow, in order to remove sorbent particles and minimise sample preparation steps. Validation resulted in limits of quantification for all PFCAs between 0.6 and 26 ng/L. Precision was between 0.7 and 15% and mean recoveries ranged from 83 to 107%. In groundwater samples from sites impacted by per- and polyfluoroalkyl substances (PFASs), PFCA concentrations ranged from 0.056 to 2.2 µg/L. TFA and perfluorooctanoate were the predominant analytes. TFA, however, revealed a more ubiquitous occurrence and was found in concentrations between 0.045 and 17 µg/L in drinking water, groundwater and surface water, which were not impacted by PFASs.

Analysis of isothiazolinones in environmental waters by gas chromatography-mass spectrometry.

This paper describes an analytical method for the determination of five biocides of isothiazolinone type (2-methyl-3-isothiazolinone (MI), 5-chloro-2-methyl-3-isothiazolinone (CMI), 1,2-benzisothiazolinone (BIT), 2-octyl-3-isothiazolinone (OI), 4,5-dichloro-2-octyl-3-isothiazolinone (DCOI)) in environmental waters. The method is based on pre-concentration of the analytes by solid-phase extraction onto a mixture of a polymeric material and RP-C18 material and subsequent determination by gas chromatography-mass spectrometry (GC-MS). One of the target compounds (BIT) is derivatised with diazomethane after pre-concentration to improve its chromatographic performance. The method was optimised with respect to pre-concentration conditions (liquid-liquid extraction versus solid-phase extraction, solid-phase material, elution solvent and volume) and extensively validated. Applying the method to surface waters, groundwaters, and drinking waters, limits of detection between 0.01 and 0.1 microg/l could be achieved and the repeatability was below 10% for all compounds except for MI. Additional investigations showed that the stability of the isothiazolinones in environmental waters is limited and sample storage at 4 degrees C is mandatory to preserve the target biocides. First investigations of influents and effluents of a wastewater treatment plant showed that conventional wastewater treatment exhibits a high efficiency for removal of the isothiazolinones. In river waters, the target isothiazolinones could not be detected.

Small, mobile, persistent: Trifluoroacetate in the water cycle - Overlooked sources, pathways, and consequences for drinking water supply.

Elevated concentrations of trifluoroacetate (TFA) of more than 100 µg/L in a major German river led to the occurrence of more than 20 µg/L TFA in bank filtration based tap waters. Several spatially resolved monitoring programs were conducted and discharges from an industrial company were identified as the point source of TFA contamination. Treatment options for TFA removal were investigated at full-scale waterworks and in laboratory batch tests. Commonly applied techniques like ozonation or granulated activated carbon filtration are inappropriate for TFA removal, whereas TFA was partly removed by ion exchange and completely retained by reverse osmosis. Further investigations identified wastewater treatment plants (WWTPs) as additional TFA dischargers into the aquatic environment. TFA was neither removed by biological wastewater treatment, nor by a retention soil filter used for the treatment of combined sewer overflows. WWTP influents can even bear a TFA formation potential, when appropriate CF3-containing precursors are present. Biological degradation and ozonation batch experiments with chemicals of different classes (flurtamone, fluopyram, tembotrione, flufenacet, fluoxetine, sitagliptine and 4:2 fluorotelomer sulfonate) proved that there are yet overlooked sources and pathways of TFA, which need to be addressed in the future.

Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater.

Due to the lack of analytical standards the application of surrogate parameters for organofluorine detection in the aquatic environment is a complementary approach to single compound target analysis of perfluoroalkyl and polyfluoroalkyl chemicals (PFASs). The recently developed method adsorbable organically bound fluorine (AOF) is based on adsorption of organofluorine chemicals to activated carbon followed by combustion ion chromatography. This AOF method was further simplified to enable measurement of larger series of environmental samples. The limit of quantification (LOQ) was 0.77 µg/L F. The modified protocol was applied to 22 samples from German rivers, a municipal wastewater treatment plant (WWTP) effluent, and four groundwater samples from a fire-fighting training site. The WWTP effluent (AOF = 1.98 µg/L F) and only three river water samples (AOF between 0.88 µg/L F and 1.47 µg/L F) exceeded the LOQ. The AOF levels in a PFASs plume at a heavily contaminated site were in the range of 162 ± 3 µg/L F to 782 ± 43 µg/L F. In addition to AOF 17 PFASs were analyzed by high performance liquid chromatography-tandem mass spectrometry. 32-51% of AOF in the contaminated groundwater samples were explained by individual PFASs wheras in the surface waters more than 95% remained unknown. Organofluorine of two fluorinated pesticides, one pesticide metabolite and three fluorinated pharmaceuticals was recovered as AOF by >50% from all four tested water matrices. It is suggested that in the diffusely contaminated water bodies such fluorinated chemicals and not monitored PFASs contribute significantly to AOF.

Occurrence and fate of nitrification and urease inhibitors in the aquatic environment.

Nitrification and urease inhibitors (NUIs) decelerate the bacterial oxidation of nitrogen species by suppressing the activity of soil microorganisms. Thus, nitrogen losses can be limited and the efficiency of nitrogen fertilizers can be increased. After application NUI transfers to surface water may occur through leaching or surface run-off. In order to assess the occurrence of nitrification and urease inhibitors in the aquatic environment a multi-analyte high-performance liquid chromatography-mass spectrometry method was developed. 1H-1,2,4-Triazole and dicyandiamide (DCD) were detected for the first time in German surface waters. Only at a few sites 1H-1,2,4-triazole has been episodically detected with concentrations up to the µg L(-1)-range. DCD was ubiquitously present in German surface waters. An industrial site was identified as the point source of DCD being responsible for exceptionally high DCD concentrations of up to 7.2 mg L(-1) in close proximity to the point of discharge. Both compounds were also detected in at least one wastewater treatment plant effluent, but their concentrations in surface waters did not correlate with those of typical markers for domestic wastewater. Other NUIs were not detected in any of the samples. Laboratory-scale batch tests proved that 1H-1,2,4-triazole and DCD are not readily biodegradable, are not prone to hydrolysis and do not tend to adsorb onto soil particles. Ozonation and activated carbon filtration proved to be ineffective for their removal.

Analysis of iodinated X-ray contrast agents in water samples by ion chromatography and inductively-coupled plasma mass spectrometry.

In this paper, an analytical method for the determination of six iodinated X-ray contrast agents (amidotrizoic acid, iohexol, iomeprol, iopamidol, iopromide, and ioxitalamic acid), iodide, and iodate in water samples is presented. The method is based on a separation of the analytes by ion chromatography (IC) and a subsequent detection by inductively-coupled plasma mass spectrometry (ICP-MS). The method was optimised with respect to separation conditions (column type and eluent composition) and extensively validated. Without pre-concentration of the samples, limits of detection below 0.2 microg/l could be achieved whereby reproducibility was below 6% for all compounds under investigation.

Emerging nitrogenous disinfection byproducts: Transformation of the antidiabetic drug metformin during chlorine disinfection of water.

As an environmental contaminant of anthropogenic origin metformin is present in the high ng/L- up to the low µg/L-range in most surface waters. Residues of metformin may lead to the formation of disinfection by-products during chlorine disinfection, when these waters are used for drinking water production. Investigations on the underlying chemical processes occurring during treatment of metformin with sodium hypochlorite in aqueous medium led to the discovery of two hitherto unknown transformation products. Both substances were isolated and characterized by HPLC-DAD, GC-MS, HPLC-ESI-TOF, (1)H-NMR and single-crystal X-ray structure determination. The immediate major chlorination product is a cyclic dehydro-1,2,4-triazole-derivate of intense yellow color (Y; C4H6ClN5). It is a solid chlorimine of limited stability. Rapid formation was observed between 10 °C and 30 °C, as well as between pH 3 and pH 11, in both ultrapure and tap water, even at trace quantities of reactants (ng/L-range for metformin, mg/L-range for free chlorine). While Y is degraded within a few hours to days in the presence of light, elevated temperature, organic solvents and matrix constituents within tap water, a secondary degradation product was discovered, which is stable and colorless (C; C4H6ClN3). This chloroorganic nitrile has a low photolysis rate in ambient day light, while being resistant to heat and not readily degraded in the presence of organic solvents or in the tap water matrix. In addition, the formation of ammonia, dimethylamine and N,N-dimethylguanidine was verified by cation exchange chromatography.

Occurrence of aminopolycarboxylates in the aquatic environment of Germany.

Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 1,3-propylenediaminetetraacetic acid (1,3-PDTA), beta-alaninediacetic acid (beta-ADA), and methylglycinediacetic acid (MGDA), are used in large quantities in a broad range of industrial applications and domestic products in order to solubilize or inactivate various metal ions by complex formation. Due to the wide field of their application, their high polarity and partly low degradability, these substances reach the aquatic environment at considerable concentrations (in the microg/L-range) and have also been detected in drinking water. This review evaluates and summarizes the results of long-term research projects, monitoring programs, and published papers concerning the pollution of the aquatic environment by aminopolycarboxylates in Germany. Concentrations and loads of aminopolycarboxylates are presented for various types of water including industrial and domestic waste waters, surface waters (rivers and lakes), raw waters, and drinking waters.

Homologue specific analysis of a polyether trisiloxane surfactant in German surface waters and study on its hydrolysis.

The occurrence of a polyether trisiloxane surfactant in the ng L(-1) range in German surface waters is reported for the first time. The studied surfactant does not ubiquitously occur in the aquatic environment but can reach surface waters on a local scale. As a first step towards the understanding of the environmental fate, the hydrolysis was studied according to the OECD guideline 111. It confirmed that the trisiloxane surfactant is sensitive to hydrolysis and that the hydrolysis rate strongly depends on the pH and the temperature. If one takes only into account the hydrolysis, the trisiloxane surfactant could persist several weeks in river water (the half-life in water is approximately 50 days at pH 7, 25 °C, and an initial concentration of 2 mg L(-1)). A degradation product, more polar than the initial trisiloxane surfactant, was identified by high resolution mass spectrometry.

Transformation of the artificial sweetener acesulfame by UV light.

The transformation of the artificial sweetener acesulfame by direct photolysis was investigated at various pH values, in different water types and at various concentration levels. Main photodegradation products of acesulfame were elucidated and analyzed both in laboratory experiments and in a full-scale waterworks using UV treatment for disinfection purposes. The degradation of acesulfame was found to be independent of the pH (range 5-11) and followed pseudo first order kinetics in a concentration range between 1 µg∙L(-1) and 10 mg∙L(-1). Calculated rate constants were in the range between 5.4·10(-3)s(-1) and 7.4·10(-3)s(-1). The main photodegradation products of acesulfame were separated by ion exchange chromatography and high performance liquid chromatography and were identified as hydroxylated acesulfame and iso-acesulfame by high resolution mass spectrometry and fragmentation experiments. In the case of iso-acesulfame an intramolecular rearrangement is assumed as the transformation product has a higher polarity and different product ions after MS fragmentation compared to acesulfame. Minor transformation products were identified as amidosulfonic acid and sulfate by comparison with analytical standards. The transformation pathway was found to be transferable to drinking water production as the identified transformation products were also detected to a similar extent in fortified tap water. In a Swiss full-scale waterworks acesulfame concentrations were reduced by approximately 30% and one of the main UV transformation products could be qualitatively detected.

Determination of adsorbable organic fluorine from aqueous environmental samples by adsorption to polystyrene-divinylbenzene based activated carbon and combustion ion chromatography.

A new method for the determination of trace levels of adsorbable organic fluorine (AOF) in water is presented. Even if the individual contributing target compounds are widely unknown, this surrogate parameter is suited to identify typical organofluorine contaminations, such as with polyfluorinated chemicals (PFCs), and represents a lower boundary of the organofluorine concentration in water bodies. It consists of the adsorption of organofluorine chemicals on a commercially available synthetic polystyrene-divinylbenzene based activated carbon (AC) followed by analysis of the loaded AC by hydropyrolysis combustion ion chromatography (CIC). Inorganic fluorine is displaced by excess nitrate during the extraction step and by washing the loaded activated carbon with an acidic sodium nitrate solution. Due to its high purity the synthetic AC had a very low and reproducible fluorine blank (0.3 µg/g) compared to natural ACs (up to approximately 9 µg/g). Using this AC, fluoride and the internal standard phosphate could be detected free of chromatographic interferences. With a sample volume of 100 mL and 2× 100 mg of AC packed into two extraction columns combined in series, a limit of quantification (LOQ), derived according to the German standard method DIN 32645, of 0.3 µg/L was achieved. The recoveries of six model PFCs were determined from tap water and a municipal wastewater treatment plant (WWTP) effluent. Except for the extremely polar perfluoroacetic acid (recovery of approximately 10%) the model substances showed fairly good (50% for perfluorobutanoic acid (PFBA)) to very good fluorine recoveries (100±20% for perfluorooctanoic acid (PFOA), perfluorobutanesulfonate (PFBS), 6:2 fluorotelomersulfonate (6:2 FTS)), both from tap water and wastewater matrix. This new analytical protocol was exemplarily applied to several surface water and groundwater samples. The obtained AOF values were compared to the fluorine content of 19 target PFCs analyzed by high performance liquid chromatography-electrospray tandem mass spectrometry (HPLC-(-)ESI-MS/MS). In groundwater contaminated by PFC-containing aqueous film-forming foams (AFFFs) up to 50% of the AOF could be attributed to PFC target chemicals, while in diffuse contaminated samples only <5% of the AOF could be identified by PFC analysis.

Development of a liquid chromatography tandem mass spectrometry method for trace analysis of trisiloxane surfactants in the aqueous environment: an alternative strategy for quantification of ethoxylated surfactants.

Trisiloxane surfactants, often referred to as superspreaders or superwetters, are added to pesticides to enhance the activity and the rainfastness of the active substance by promoting rapid spreading over hydrophobic surfaces. To fill the lack of data on the environmental occurrence of these compounds, we have developed and validated a method for their trace analysis in the aqueous environment. The method is based on liquid-liquid extraction followed by liquid chromatography and tandem mass spectrometry. The oligomeric distribution of trisiloxane surfactant in a reference solution was determined by a theoretical calculation and by experimental measurements. Based on these results, the quantification was performed by comparison with a calibration made with a single homologue instead of a mixture of homologues. This approach avoids a time-consuming synthesis of pure homologues and reduces the risk of wrong estimation of the concentration because of different response factors of the sample and the standard. Such an approach could be applied to the quantification of other ethoxylated surfactants following a similar distribution. The validation was performed from 2 to 250 ng/L (total surfactant concentration) in deionized water, tap water, and river water (Rhine water). Knowing the oligomeric distribution of the polymer in the reference solution, the corresponding calibration ranges were estimated for individual homologues. Limits of quantification were found to be between 0.37 ng/L and 15 ng/L. The total recovery of sample preparation was between 77% and 116%. Matrix effects were lower than 10% with river water and the relative standard deviation evaluated over ten identical samples of spiked river water was below 12%.

Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment.

Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 µg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of µg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 µg/L for metformin and several µg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 µg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.

Structural elucidation of main ozonation products of the artificial sweeteners cyclamate and acesulfame.

PURPOSE: The two artificial sweeteners cyclamate (CYC) and acesulfame (ACE) have been detected in wastewater and drinking water treatment plants. As in both facilities ozonation might be applied, it is important to find out if undesired oxidation products (OPs) are formed. METHODS: For the separation and detection of the OPs, several analytical techniques, including nuclear magnetic resonance experiments, were applied. In order to distinguish between direct ozone reaction and a radical mechanism, experiments were carried out at different pH values with and without scavenging OH radicals. Kinetic experiments were used for confirmation that the OPs are formed during short ozone contact time applied in waterworks. Samples from a waterworks using bank filtrate as raw water were analyzed in order to prove that the identified OPs are formed in real and full-scale ozone applications. RESULTS: In the case of CYC, oxidation mainly occurs at the carbon atom, where the sulfonamide moiety is bound to the cyclohexyl ring. Consequently, amidosulfonic acid and cyclohexanone are formed as main OPs of CYC. When ozone reacts at another carbon atom of the ring a keto moiety is introduced into the CYC molecule. Acetic acid and the product ACE OP170, an anionic compound with m/z=170 and an aldehyde hydrate moiety, were identified as the main OPs for ACE. The observed reaction products suggest an ozone reaction according to the Criegee mechanism due to the presence of a C=C double bond. ACE OP170 was also detected after the ozonation unit of a full-scale drinking water treatment plant which uses surface water-influenced bank filtrate as raw water. CONCLUSIONS: Acesulfame can be expected to be found in anthropogenic-influenced raw water used for drinking water production. However, when ACE OP170 is formed during ozonation, it is not expected to cause any problem for drinking water suppliers, because the primary findings suggest its removal in subsequent treatment steps, such as activated carbon filters.

N,N-dimethylsulfamide as precursor for N-nitrosodimethylamine (NDMA) formation upon ozonation and its fate during drinking water treatment.

Application and microbial degradation of the fungicide tolylfluanide gives rise to a new decomposition product named N,N-dimethylsulfamide (DMS). In Germany, DMS was found in groundwaters and surface waters with typical concentrations in the range of 100-1000 ng/L and 50-90 ng/L, respectively. Laboratory-scale and field investigations concerning its fate during drinking water treatment showed that DMS cannot be removed via riverbank filtration, activated carbon filtration, flocculation, and oxidation or disinfection procedures based on hydrogen peroxide, potassium permanganate, chlorine dioxide, or UV irradiation. Even nanofiltration does not provide a sufficient removal efficiency. During ozonation about 30-50% of DMS are converted to the carcinogenic N-nitrosodimethylamine (NDMA). The NDMA being formed is biodegradable and can at least partially be removed by subsequent biologically active drinking water treatment steps including sand or activated carbon filtration. Disinfection with hypochlorous acid converts DMS to so far unknown degradation products but not to NDMA or 1,1-dimethylhydrazine (UDMH).